首页> 外文OA文献 >A Cation-Captured Palladium(0) Anion: Synthesis, Structure, and Bonding of [PdBr(PPh3)2]− Ligated by an N-Heterocyclic Phosphenium Cation
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A Cation-Captured Palladium(0) Anion: Synthesis, Structure, and Bonding of [PdBr(PPh3)2]− Ligated by an N-Heterocyclic Phosphenium Cation

机译:阳离子捕获的钯(0)阴离子:由N-杂环磷阳离子连接的[PdBr(PPh3)2]-的合成,结构和键合

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摘要

Unsaturated N-heterocyclic phosphenium cations (uNHP) stabilize the [Pd0(PR3)2X]− anion proposed over the past decade to be the crucial but elusive intermediate in palladium-catalyzed cross-coupling reactions (X = halide). Insertion of metal into the P−Br bond of the precursor mesityl-substituted bromophosphine gives the structurally characterized Pd(0)-phosphenium complex (uNHPMes)Pd(PPh3)2Br, which features a long Pd−Br bond (2.7240(9) Å) and the shortest known Pd−P bond (2.1166(17) Å). The reaction is proposed to proceed by an associative pathway involving a Pd-bromophosphine complex that undergoes P-to-Pd bromide transfer.
机译:不饱和的N杂环phosph阳离子(uNHP)稳定了过去十年中提出的[Pd0(PR3)2X]-阴离子,这是钯催化的交叉偶联反应中至关重要但难以捉摸的中间体(X =卤化物)。将金属插入前体甲基取代的溴膦的P-Br键中可得到结构特征化的Pd(0)-complex络合物(uNHPMes)Pd(PPh3)2Br,其特征在于长的Pd-Br键(2.7240(9)Å )和已知最短的Pd-P键(2.1166(17)Å)。提出该反应通过涉及P-溴膦复合物的缔合途径进行,所述Pd-溴膦复合物经历P-Pd-溴转移。

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